Thiazyl sulphenamide derivatives



Patented June 13, 1944 UNITED STATES PATENT OFFICE THIAZYL SULPHENAMIDE DERIVATIVES William H. Ebelke, Naugatuck, Co-nn., assignor to United States Rubber Company, New York, N. Y., a corporation of New Jersey No Drawing. Original application November 23,

1940, Serial No. 366,885. Divided and this application November 27, 1941, Serial No. 420,678

5 Claims.

where X is sulphur or oxygen; Y and Z are hydrogen, alkyl, alkenyl, aryl, aralkyl, or alkylene radicals of a heterocylic group with the N. The aryl, and aralkyl may also contain substituents such as halogen, alkyl, hydroxy, nitro, etc.

The thiazyl sulphur halide may be prepared in solution by passing a halogen, e. g. dry chlorine, into a. suspension or slurry of the 1,1'-dithio bis thiazole (illustrated by 1,1'-dithio bis benzothiazole) in an organic solvent such as benzene, tetrachloro ethylene, carbon tetrachloride, etc., which is unreactive With the halogen, until substantially complete solution ensues. After heating to remove excess halogen, the hot solution is freed of insoluble matter and cooled. The thiazyl sulphur halide has the general formula X, YQZ beingas above stated; and T representing a l-thiazyl radical, preferably a l-arylene thiazyl radical. The thiazyl radical may contain various substituents such as hydrogen, halogen, alkyl, aralkyl, aryl, alicyclic, alkoxy, or aryloXy radicals.

. The following are given as representative examp-les:

N-(carbamyl) benzothiazyl sulphenamide N-(thio carbamyl) 'benzothiazyl sulphenamide irN-(phenyl carbamyl) benzothiazyl sulphenamide N-(phenyl thiocarbamyl) benzothiazyl sulphenamide N-(methyl carbamyl) benzothiazyl sulphenamide N-(methyl thiocarbamyl) benzothiazyl sulphenamide N-(tolyl carbamyl) benzothiazyl sulphenamide N-(tolyl thiocarbamyl) .benzothiazyl sulphenamide N-(diphenyl carbamyl) benzothiazyl .sulphen-' 2o- 1 -N-(nitrophenyl thiocarbamyl) benzothiazyl sulphenamide N-(carbamyl) thiazyl sulphenamide N-(phenyl carbamyl) thiazyl sulphenamide N-(thiocarbamyl') thiazyl sulphenamide -N-(phenyl thiocarbamyl) thiazyl sulphenamide N-(carbamyl) methyl thiazyl sulphenamide N-(thiocarbamyl) methyl thiazyl sulphenamide N-(phenylcarbamyl) methyl thiazyl sulphenamide N-(carbamyl) dihydrothiazyl sulphenamide N-(piperidyl carbonyl) dihydrothiazyl sulphenamide N-(morp-holyl carbonyl) benzothiazyl sulphenamide N-(morpholyl carbonyl) thiazyl sulphenamide N-(morpholyl carbonyl) methyl thiazyl sulphenamide N-(morpholyl thiocarbonyl) methyl thiazyl sulphenamide Illustrative of their preparation and use in benzothiazyl sulphenrubber as vulcanizing accelerators are the following examples, the parts being by weight:

EXAMPLE 1 Preparation of N-(carbamyl) benzothiazyl sulphenamide Percent Nitrogen foun 17.0 Nitrogen theory 18.6

Sulphur found 28.4 Sulphur theory 26.8

On purification, a snow white powder was obtained, M. R. 195-196 C. with decomposition.

Percent Nitrogen found 17.9 Nitrogen theory 18.6

Sulphur found 28.5 Sulphur theory 28.6

The product (M. R. 182-186 C. with decompositlon) was incorporated into the following rubber stock, vulcanized and tested.

Master batch Smoked sheet 10 Carbon hlar'k 45 Zinc oxide 5 Pine tar 3.50 Zinc soap of cocoanut oil acids 3.50 Acetone-diphenylamine condensate (antioxidant) 1.00 Sulphur 3.00

161.00 Recipes 7 Above master batch 161 161 161 Mercaptobenzothiazole 0. 8 1. 0 N-(carbamyl) benzothiazyl sulphenamidc Tensiles .I N G B E B E B E 4, 200-736 4,540-743 4,680-710 4,620680 4,600-680 4,660-673 4,5soe43 4,620-65O AGED 96 HOURS IN OXYGEN 457 2,330-646 2, 630-666 2, sac-e60 B=Break.

It is apparent that this chemical closely resembles mercaptobenzothiazole in strength. It also shows a definite advantage over the latter in that it gives more delayed action and so is safer to use because it does not tend to pre-cure the rubber during processing of the same.

EXAMPLE 2 Preparation of N-(phenyl carbamyl) benzothiazyl sulphenamid'e 7 Percent Nitrogen found 13.0 Nitrogen theory 13.9

Sulphur found g 21.8 Sulphur theory 21.3 V

The following rubber stock was made up and tested:

Master batch. i Smoked shee 100, Carbon black 45 Zinc oxide 5 Pine tar 3.5 Zinc soap of cocoanut oil acids 3.5

Recipes- 1 Above master batch 160 Mercaptobenzothiazole 1.0 N(phenyl carbamyl) benzothiazyl sulphenamide 1.0

Tensiles UNAGED B e E B s 4, 200-630 4,200-5s3 4,300-560 4,1sa-530 45'/s0# +4. 5 1.9 60/30# -s. s -7. 6 7573019 -11.3 -12. 7 90'/ao# -16. 5 l6. 5

soonon TEST l,176 25a -1,020 ISO-1,136 750-843 l70-1,090 1,183-753 1631,023 1,537-667 17o-1,03a 1,945-687 200-1, 35 2, 513696 Obviously N-(phenyl carbamyl) benzothlazyl sulphenamide is an excellent accelerator and is superior to mercaptobenzothiazole in, safety from. '1

,precure. a

EXAMPLE 3 Preparation of N-(thz'ocarbamyl) benzothiazyl sulphenamide This chemical is prepared by a procedure similar to that used in Example 1. The product is a light yellow powder, M. R. 136141 C.

Per cent Sulphur found 40.8 Sulphur theory 39.80

N- (thiocarbamyl) benzothiazyl sulphenamide was tested in rubber to give the following results:

Master batch Acetone-diphenylamine condensate (antioxidant) 1.00

161.00 Recipes Above master batch 161 161 Merczptobenzothiezole 1.0 N-(thiocarbamyl) benzothiazyl sulphenamlde .l 1.0

Tensiles UNAGED B E B E AGED 96 HOURS AT 212 F.

B=Break E=E1ongation.

T-50 AT 350 PER CENT The chemicals may be employed in the vulcanization of rubber generally. The rubber may be masticated with other compounding and vulcanizing ingredients, or be in the form of a vulcanizable latex composition (natural or artificially prepared), or in the form of a deposit from such latex compositions.

The chemicals may be used alone, in conjunction with other accelerators such as mercaptobenzothiazole, or in conjunction with activating more basic nitrogen compositions such as diphenylguanidine.

The present invention is not limited in its use to the specific examples above set forth wherein the preferred accelerators are employed. Other ratios of the compounding ingredient than those mentioned in the examples as well as other well known fillers, pigments, etc. may be employed in the production of various types of rubber compounds as will. be apparent to those skilled in the art.

The chemicals may also find use as pharmaceuticals, or intermediates in chemical synthesis.

Having thus described my invention, what I claim and desire to protect by Letters Patent is:

l. A method which comprises vulcanizing rubber with N-(carbamyl) benzothiazyl sulphenamide. I

2. A method which comprises vulcanizing rubber with N-(thiocarbamyl) benzothiazyl sulphenamide.

3. A method which comprises vulcanizing rubber with N- (phenyl carbamyl) benzothiazyl sulphenamide.

4. A method which comprises vulcanizing rubber with a benzothiazyl sulphenamide in which one of the amine hydrogen atoms is replaced by the group III-Y Z where X is a member selected from the group consisting of sulphur, and oxygen; Y and Z are radicals selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl, aryl, and alkylene radicals of a heterocyclic ring embodying the N.

5. A vulcanization product of rubber containing a compound having the formula III-Y Z wherein X is a member selected from the group consisting of sulphur, and oxygen; T is a l-thiazyl radical; Y and Z are radicals selected from the group consisting of hydrogen, alkyl, alkenyl, aralkyl, aryl, and alkylene radicals of a heterocyclic ring embodying the N.

WILLIAM H. EBELKE. 

